CN114832643A - Preparation method of high-strength long-acting antioxidant polyvinylidene fluoride hollow fiber membrane - Google Patents
Preparation method of high-strength long-acting antioxidant polyvinylidene fluoride hollow fiber membrane Download PDFInfo
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- CN114832643A CN114832643A CN202210524337.7A CN202210524337A CN114832643A CN 114832643 A CN114832643 A CN 114832643A CN 202210524337 A CN202210524337 A CN 202210524337A CN 114832643 A CN114832643 A CN 114832643A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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Abstract
The invention relates to a preparation method of a high-strength long-acting antioxidant polyvinylidene fluoride hollow fiber membrane, which comprises the following steps: at the temperature of 100-250 ℃, placing polyvinylidene fluoride resin, an anchoring agent and a gelling agent in a diluent, dissolving uniformly and defoaming to obtain a casting solution; extruding the membrane casting solution into a hollow fiber membrane blank, passing through an air section with the diameter of 2-10 mm, entering a cooling bath containing inorganic sol for curing and forming, and cleaning and airing. The gel added in the invention can form a cross-linked network with polyvinylidene fluoride in the membrane, thereby improving the strength of the membrane; the added anchoring agent can migrate to the surface in the process of curing and forming and is in coordination coupling with the nano sol particles to form a strong inorganic antioxidant protective layer. The cross section of the hollow fiber membrane prepared by the method is of a double-network cross-linked structure, so that the hollow fiber membrane is endowed with high strength; the surface of the membrane is provided with a nano material functional layer, so that the membrane has the performances of oxidation resistance, hydrophilicity and the like, and the functional layer has better stability.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a high-strength long-acting antioxidant polyvinylidene fluoride hollow fiber membrane and a preparation method thereof.
Background
Polyvinylidene fluoride hollow fiber membrane, packing density is big, and filtration efficiency is high, has excellent chemistry and thermal stability, uses extensively in fields such as municipal sewage, industrial waste water, industrial water supply, municipal water supply, domestic water purification. The existing preparation method of the polyvinylidene fluoride membrane has the defects of no oxidation resistance, insufficient membrane strength and easy pollution.
Disclosure of Invention
Aiming at the problems existing in the preparation of polyvinylidene fluoride hollow fiber membranes in the prior art, the invention provides a preparation method of a high-strength long-acting antioxidant polyvinylidene fluoride hollow fiber membrane, which can be used for preparing a high-strength long-acting antioxidant polyvinylidene fluoride membrane, so that the membrane surface has a nano material functional layer, the membrane is endowed with performances of oxidation resistance, hydrophilicity and the like, and the functional layer has better stability. The invention can greatly improve the effect and efficiency of the membrane method in water treatment, and promote better solution of the problems of water environment pollution treatment and water resource shortage.
The invention is realized by the following steps:
a preparation method of a high-strength long-acting antioxidant polyvinylidene fluoride hollow fiber membrane comprises the following steps:
step S1: at the temperature of 100-250 ℃, 25-50wt% of polyvinylidene fluoride resin; 5-10wt% of an anchoring agent; 1-5% of gelling agent; uniformly dissolving 35-69 wt% of a diluent and defoaming to obtain a casting solution;
step S2: preparing core liquid, wherein one or two of water, glycerol, propylene glycol, 1-octanol, glycerol triacetate, polyethylene glycol, nitrogen, polypropylene glycol and air are used as core liquid materials;
and step S3, extruding the prepared membrane casting solution and core solution into a hollow fiber membrane blank through a spinning jet, passing through an air section with the diameter of 2-10 mm, entering a cooling bath containing inorganic sol for phase separation and solidification forming, cleaning and airing to obtain the usable high-strength long-acting antioxidant polyvinylidene fluoride hollow fiber membrane material.
Preferably, the polyvinylidene fluoride resin is one or more of polyvinylidene fluoride powder, granules or flaky materials with the weight average molecular weight of 50-90 ten thousand.
Preferably, the anchoring agent is one or more of phenyl cyclic amide, toluene sulfonic acid acetamide, toluene sulfonic acid butyramide, alkyl sulfonic acid phenol, 4-fluorobenzene sulfonamide, perfluoro octyl cyclic amide, 2- (trifluoromethoxy) benzene sulfonamide.
Preferably, the gelling agent is one or more of allyl phthalate, dibutyl fumarate, dibutyl itaconate diethyl maleate and triallyl cyanurate.
Preferably, the diluent is one or more of 2-ethylhexyl terephthalate, ethyl phthalate-ethyl glycolate, mixed esters of phthalic acid C4-C5, diethylene glycol abietate and pentaerythritol fatty acid ester.
Preferably, the inorganic material configured with the nano sol is one or a combination of more than two of silicon dioxide, titanium dioxide, aluminum oxide, copper oxide, zinc oxide, montmorillonite and basalt.
Preferably, the coagulating bath is a solvent capable of forming a sol with the inorganic nanomaterial, such as one or a combination of two of water, glycerol, triethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol, and polyethylene glycol.
Preferably, the inner diameter of the core liquid extrusion channel of the spinneret is 0.3-0.6 mm; the inner diameter of the layer is 0.5-0.8 mm, the outer diameter is 1.1-1.4 mm, and the width of the gap of the casting solution channel is controlled to be 0.2-0.4 mm.
Preferably, the phase separation of step S3 is thermally induced phase separation.
In the invention, under the action of high dissolving temperature, the dissolving property of the polyvinylidene fluoride can be obviously enhanced. Therefore, by increasing the dissolution temperature, more polyvinylidene fluoride resin can be dissolved than by using a high temperature diluent compared to dissolution at low temperature, resulting in a high solid content, high viscosity polyvinylidene fluoride casting solution, which is critical to promoting the strength of the membrane. The polyvinylidene fluoride mass fraction set by the invention is 25-50wt%, and in the range, the polyvinylidene fluoride can be uniformly dissolved under the set diluent and temperature system on the premise of ensuring high strength. The mass fraction is too high, more than 50wt%, and besides being difficult to dissolve, the water permeability of the prepared membrane is remarkably reduced, so that the operation treatment capacity of the membrane cannot be ensured. If the mass fraction is too low, less than 25wt%, the strength of the membrane is significantly reduced, so that the mass fraction of polyvinylidene fluoride suitable for the present invention is 25wt% to 50wt%, preferably 30 wt% to 40 wt%.
In the invention, the gel contains reactive groups, and when the gel is added into polyvinylidene fluoride, the gel and the polyvinylidene fluoride can be combined on polyvinylidene fluoride molecules by chemical bonds, or cross-linked with each other to form a team structure, or self-polymerized and intertwined with the polyvinylidene fluoride under certain conditions, so that the mechanical strength of a polyvinylidene fluoride network is obviously improved.
In the present invention, the anchoring agent is a cyclic amide-containing compound capable of anchoring the inorganic nanomaterial on the surface of the polyvinylidene fluoride membrane in the form of a coordinate bond. The selected inorganic nano material is not only hydrophilic, but also has strong oxidation resistance, ultraviolet resistance and other properties. Therefore, after the inorganic nano materials are stably fixed on the surface of the polyvinylidene fluoride, the hydrophilic oxidation resistance of the polyvinylidene fluoride can be remarkably improved.
On one hand, polyvinylidene fluoride with high solid content is used and matched with a gelling agent to obtain a high-strength polyvinylidene fluoride film layer; on the other hand, the inorganic hydrophilic antioxidant nano material is fixed by adopting a cyclic amide anchoring agent in a form of coordinate bonds, so that the polyvinylidene fluoride hollow fiber membrane has hydrophilic antioxidant performance. The invention innovatively adopts an organic/inorganic composite method, so that the polyvinylidene fluoride hollow fiber membrane has high strength and hydrophilic oxidation resistance, the stability of the polyvinylidene fluoride hollow fiber membrane in water treatment is greatly improved, and the service life of the polyvinylidene fluoride hollow fiber membrane is obviously prolonged.
Drawings
FIG. 1 is a schematic cross-sectional structure view of a polyvinylidene fluoride hollow fiber membrane prepared by the present invention;
FIG. 2 is a schematic view of the surface structure of the polyvinylidene fluoride hollow fiber membrane prepared by the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, and it should be understood that the described examples are only a part of the examples of the present invention, and not all of the examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A preparation method of a high-strength long-acting antioxidant polyvinylidene fluoride hollow fiber membrane comprises the following steps:
(1) at the temperature of 100-250 ℃, placing 25-50wt% of polyvinylidene fluoride resin, 5-10wt% of anchoring agent and 1-5wt% of gelling agent in 35-69 wt% of diluent, dissolving uniformly and defoaming to obtain the casting solution.
(2) And preparing the core liquid at room temperature for forming the cavity of the hollow fiber membrane.
(2) And extruding the prepared core solution and the casting solution from the inner side and the outer side of a spinning nozzle respectively to form a hollow fiber membrane blank, passing through an air section of 2-10 mm, entering a cooling bath containing inorganic sol to carry out phase separation and solidification forming, and washing and drying to obtain the usable high-strength long-acting antioxidant polyvinylidene fluoride hollow fiber membrane material.
Preferably, in step (1): the mass fraction of the polyvinylidene fluoride resin is 25-50wt%, preferably 30-45wt%, more preferably 35-40 wt%; the mass fraction of the anchoring agent is 5-10wt%, preferably 6-8 wt%; the mass fraction of the gelling agent is 1-5wt%, preferably 2-4 wt%; the dissolution temperature is 100-250 ℃, preferably 150-230 ℃, and more preferably 180-220 ℃.
Preferably, in step (1): the polyvinylidene fluoride resin is one or a mixture of more than two of polyvinylidene fluoride powder, granules or flaky materials with the weight average molecular weight of 50-90 ten thousand; the weight average molecular weight is preferably 60 to 80 ten thousand, more preferably 60 to 70 ten thousand. The shape is preferably a pellet.
Preferably, in step (1): the gel is one or a combination of allyl phthalate, dibutyl fumarate, dibutyl itaconate diethyl maleate and triallyl cyanurate.
Preferably, in step (1): the anchoring agent is one or more of phenyl cyclic amide, toluene sulfonic acid acetamide, toluene sulfonic acid butyramide, alkyl sulfonic acid phenol, 4-fluorobenzene sulfonamide, perfluorooctyl cyclic amide and 2- (trifluoromethoxy) benzene sulfonamide.
Preferably, in step (1): the diluent is one or a combination of more of 2-ethylhexyl terephthalate, ethyl phthalate and ethyl glycolate, mixed esters of phthalic acid C4-C5, diethylene glycol abietate and pentaerythritol fatty acid ester.
Preferably, in the step (2), the bore fluid is one or two of water, glycerol, propylene glycol, 1-octanol, glycerol triacetate, polyethylene glycol, nitrogen, polypropylene triol and air. Water, glycerin, nitrogen, and air are preferred as the bore fluid.
Preferably, in the step (3), the inner diameter of the core liquid extrusion channel of the spinneret is 0.3-0.6 mm; the inner diameter of the layer is 0.5-0.8 mm, the outer diameter is 1.1-1.4 mm, and the width of the gap of the casting solution channel is controlled to be about 0.3 mm. Preferably, the diameter of the core liquid channel is 0.6 mm, the inner diameter and the outer diameter of the liquid extrusion channel are 0.7 mm and 1.3 mm respectively, namely, the gap is 0.3 mm.
Preferably, in the step (3), the inorganic material for preparing the nano sol is one or a combination of two or more of silica, titanium dioxide, alumina, copper oxide, zinc oxide, montmorillonite and basalt, preferably silica, titanium dioxide and alumina, and more preferably silica and titanium dioxide.
Preferably, in step (3), the cooling bath is a solvent capable of forming a sol with the inorganic nanomaterial, such as one or a combination of two of water, glycerol, triethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polypropylene triol, and polyethylene glycol. Preferably and most preferably, water is the cooling bath and the temperature is controlled to be less than 5 ℃.
As can be seen from the figures 1 and 2, the high-strength long-acting antioxidant polyvinylidene fluoride hollow fiber membrane prepared by the method disclosed by the invention is shown by the following performance indexes: the tensile strength is more than 10N, the breaking elongation is more than 120%, the average pore diameter is 0.1-0.2 micrometer, the external pressure pure water flux reaches more than 1000L/m per hour (1 bar, 25 ℃), the internal pressure pure water flux reaches more than 2000L/m per hour (1 bar, 25 ℃), the porosity is more than 60%, the average water contact angle is reduced to less than 42 ℃, the sodium hypochlorite, the sodium hydroxide, the hydrochloric acid and the sulfuric acid which are 10% and 1% hydrogen peroxide can be completely soaked in 10 seconds, the sodium hypochlorite, the sodium hydroxide, the hydrochloric acid and the sulfuric acid which are not less than 5000ppm in concentration can be tolerated, the sodium hypochlorite, the sodium hydroxide, the hydrochloric acid and the sulfuric acid and the hydrogen peroxide which are 1 mg/l per day can be used for cleaning, the ozone radiation sterilization and disinfection are performed, and all the comprehensive performances are excellent.
Claims (9)
1. A preparation method of a high-strength long-acting antioxidant polyvinylidene fluoride hollow fiber membrane is characterized by comprising the following steps
The method comprises the following steps:
step S1: at the temperature of 100-250 ℃, 25-50wt% of polyvinylidene fluoride resin; 5-10wt% of an anchoring agent; 1-5% of gelling agent; uniformly dissolving 35-69 wt% of a diluent and defoaming to obtain a casting solution;
step S2: preparing core liquid, wherein one or two of water, glycerol, propylene glycol, 1-octanol, glycerol triacetate, polyethylene glycol, nitrogen, polypropylene glycol and air are used as core liquid materials;
step S3: and extruding the prepared membrane casting solution and core solution through a spinning nozzle to form a hollow fiber membrane blank, passing through an air section with the diameter of 2-10 mm, entering a cooling bath containing inorganic sol to perform phase separation and solidification molding, and cleaning and drying to obtain the usable high-strength long-acting antioxidant polyvinylidene fluoride hollow fiber membrane material.
2. The method of claim 1, wherein: the polyvinylidene fluoride resin is one or a mixture of polyvinylidene fluoride powder, granules or flaky materials with the weight average molecular weight of 50-90 ten thousand.
3. The production method according to claim 1 or 2, characterized in that: the anchoring agent is one or more of phenyl cyclic amide, toluene sulfonic acid acetamide, toluene sulfonic acid butyramide, alkyl sulfonic acid phenol, 4-fluorobenzene sulfonamide, perfluorooctyl cyclic amide and 2- (trifluoromethoxy) benzene sulfonamide.
4. The production method according to claim 1 or 2, characterized in that: the gel is one or more of allyl phthalate, dibutyl fumarate, dibutyl itaconate diethyl maleate and triallyl cyanurate.
5. The production method according to claim 1 or 2, characterized in that: the diluent is selected from 2-ethylhexyl terephthalate, ethyl glycolate, and C phthalate 4 ~C 5 One or more of mixed ester, diethylene glycol abietate and pentaerythritol fatty acid ester.
6. The production method according to claim 1 or 2, characterized in that: the inorganic material for preparing the nano sol is one or the combination of more than two of silicon dioxide, titanium dioxide, aluminum oxide, copper oxide, zinc oxide, montmorillonite and basalt.
7. The production method according to claim 1 or 2, characterized in that: the coagulating bath is a solvent capable of forming a sol with the inorganic nano material, such as one or two of water, glycerol, triethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polypropylene triol and polyethylene glycol.
8. The production method according to claim 1 or 2, characterized in that: the inner diameter of the core liquid extrusion channel of the spinning nozzle is 0.3-0.6 mm; the inner diameter of the layer is 0.5-0.8 mm, the outer diameter is 1.1-1.4 mm, and the width of the gap of the casting solution channel is controlled to be 0.2-0.4 mm.
9. The production method according to claim 1 or 2, characterized in that: the phase separation described in step S3 is a thermally induced phase separation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115382396A (en) * | 2022-08-15 | 2022-11-25 | 无锡零界净化设备股份有限公司 | Preparation method of casting solution of hydrophilic PVDF (polyvinylidene fluoride) microporous filter membrane |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060230926A1 (en) * | 2005-04-13 | 2006-10-19 | Gkss-Forschungszentrum Geesthacht Gmbh | Composite material, in particular composite membrane, and process for the production of the same |
| US20120080378A1 (en) * | 2010-09-30 | 2012-04-05 | Ravindra Revanur | Thin film composite membranes for forward osmosis, and their preparation methods |
| CN103079686A (en) * | 2010-09-02 | 2013-05-01 | 香港大学 | Doping of inorganic minerals to hydrophobic membrane surface |
| CN105727751A (en) * | 2016-04-26 | 2016-07-06 | 上海应用技术学院 | Application of high-dispersity hybridization antibacterial agent in aspect of ultrafiltration membrane improvement |
| CN105879720A (en) * | 2014-12-16 | 2016-08-24 | 江南大学 | Preparation method of heat and chemical cross-linked hyperbranched polysiloxane pervaporation membrane |
| CN111214967A (en) * | 2020-01-17 | 2020-06-02 | 天津生态城水务投资建设有限公司 | Preparation method of high-performance ZIF-8-containing nanofiltration membrane based on two-step addition of sodium polystyrene sulfonate |
| CN112246111A (en) * | 2020-10-11 | 2021-01-22 | 天津工业大学 | Preparation method of metal organic framework film |
| CN112337323A (en) * | 2020-09-28 | 2021-02-09 | 南京工业大学 | PVDF (polyvinylidene fluoride) polymer separation membrane and preparation method thereof |
| CN112870985A (en) * | 2021-01-15 | 2021-06-01 | 浙江工业大学 | Method for preparing PVDF super-amphiphilic oil-water separation membrane by in-situ polymerization of ion-crosslinked fixed nanoparticles and prepared membrane |
| CN113398780A (en) * | 2021-01-13 | 2021-09-17 | 杭州高通膜技术有限公司 | Preparation method of polyvinylidene fluoride hollow fiber membrane with ultrahigh tensile strength and anti-peeling strength and extrusion equipment thereof |
-
2022
- 2022-05-14 CN CN202210524337.7A patent/CN114832643B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060230926A1 (en) * | 2005-04-13 | 2006-10-19 | Gkss-Forschungszentrum Geesthacht Gmbh | Composite material, in particular composite membrane, and process for the production of the same |
| CN103079686A (en) * | 2010-09-02 | 2013-05-01 | 香港大学 | Doping of inorganic minerals to hydrophobic membrane surface |
| US20120080378A1 (en) * | 2010-09-30 | 2012-04-05 | Ravindra Revanur | Thin film composite membranes for forward osmosis, and their preparation methods |
| CN105879720A (en) * | 2014-12-16 | 2016-08-24 | 江南大学 | Preparation method of heat and chemical cross-linked hyperbranched polysiloxane pervaporation membrane |
| CN105727751A (en) * | 2016-04-26 | 2016-07-06 | 上海应用技术学院 | Application of high-dispersity hybridization antibacterial agent in aspect of ultrafiltration membrane improvement |
| CN111214967A (en) * | 2020-01-17 | 2020-06-02 | 天津生态城水务投资建设有限公司 | Preparation method of high-performance ZIF-8-containing nanofiltration membrane based on two-step addition of sodium polystyrene sulfonate |
| CN112337323A (en) * | 2020-09-28 | 2021-02-09 | 南京工业大学 | PVDF (polyvinylidene fluoride) polymer separation membrane and preparation method thereof |
| CN112246111A (en) * | 2020-10-11 | 2021-01-22 | 天津工业大学 | Preparation method of metal organic framework film |
| CN113398780A (en) * | 2021-01-13 | 2021-09-17 | 杭州高通膜技术有限公司 | Preparation method of polyvinylidene fluoride hollow fiber membrane with ultrahigh tensile strength and anti-peeling strength and extrusion equipment thereof |
| CN112870985A (en) * | 2021-01-15 | 2021-06-01 | 浙江工业大学 | Method for preparing PVDF super-amphiphilic oil-water separation membrane by in-situ polymerization of ion-crosslinked fixed nanoparticles and prepared membrane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115382396A (en) * | 2022-08-15 | 2022-11-25 | 无锡零界净化设备股份有限公司 | Preparation method of casting solution of hydrophilic PVDF (polyvinylidene fluoride) microporous filter membrane |
| CN115382396B (en) * | 2022-08-15 | 2024-02-23 | 无锡零界净化设备股份有限公司 | Preparation method of membrane casting solution of hydrophilic PVDF microporous filter membrane |
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